JP2016118759A - Charge control agent, manufacturing method of charge control agent, and toner for electrostatic charge image development including charge control agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a charge control agent that achieves quick rise of charge and can express excellent charge characteristics, and a manufacturing method of the charge control agent.SOLUTION: A manufacturing method of a charge control agent including an azo-iron complex salt includes: a reaction step of obtaining a monoazo compound by diazotized coupling reaction; a metallization step of reacting the monoazo compound with an ironizing agent to obtain a wet cake of an azo-iron complex salt; and a drying step of stirring, while heating, the wet cake of an azo-iron complex salt with a paddle to dry the wet cake.SELECTED DRAWING: None

Description

  The present invention relates to a negatively chargeable charge control agent containing an azo-based iron complex salt, a method for producing a negatively chargeable charge control agent, and an electrostatic image developing toner containing the negatively chargeable charge control agent.

  Electrophotographic systems are used for copying machines, printers, facsimiles, and the like. In this system, an electrostatic latent image is developed on a photosensitive member provided with a photosensitive layer containing an inorganic or organic photoconductive material with toner triboelectrically charged, transferred to a recording paper, and fixed.

  To increase the charging speed of the toner, to stabilize the toner sufficiently and control the amount of charge appropriately to improve the charging characteristics, to stably control the electrostatic latent image and develop at a high speed In order to form a clear and high-quality image, a charge control agent that appropriately adjusts the charge of the toner is added in advance.

  As such charge control agents, for example, Patent Document 1, Patent Document 2, and Patent Document 3 disclose azo metal complex salts having negative chargeability.

  With higher performance such as improved resolution of copiers and printers in recent years, and the expansion of applications such as low-speed development as well as high-speed development in electrophotographic systems, the rise of toner charging is further accelerated and further excellent charging characteristics Therefore, there is a need for a charge control agent that can produce a clear, high-resolution image, and that can be produced simply and with high yield, and a toner using the same. There is also a need for a charge control agent that can be used in powder coatings used in electrostatic powder coating that attracts and bakes electrostatically charged powder coatings onto the surface charge of the structure.

  The particle size and particle size distribution of the charge control agent are important factors for developing the charge characteristics of the electrostatic image developing toner. In addition to the reduction in particle size and sharpening of the particle size distribution that can support high resolution, there is an increasing demand for toner that can be used in high-speed models, and small particles with a narrow particle size distribution for the charge control agent used in the toner. There is an increasing demand for diameter reduction.

  A monoazo compound containing a naphthol AS compound as a coupling component has low solubility in water or an organic solvent. For this reason, in the metallization reaction of the monoazo compound, the monoazo compound is precipitated and metallized. Moreover, since it is a solid-solid metallization reaction, it is difficult to adjust the particle size and particle size distribution of the azo iron complex salt to desired values in the metallization reaction.

  Furthermore, the azo iron complex salt obtained by this metallization reaction is in the form of a wet cake. When a wet cake of an azo-based iron complex salt is dried using a normal shelf-type hot air dryer, a hard solid dried product is easily obtained. Therefore, when this dried product is crushed, large-sized particles tend to remain, the particle size distribution becomes broad, and it is difficult to obtain an azo-based iron complex salt having a sharp particle size distribution suitable for a charge control agent. There is a problem.

JP 61-101558 A JP-A 61-155463 Japanese Patent Laid-Open No. 62-177561

  The present invention has been made to solve the above-mentioned problems, and the rising of the charge is fast, it exhibits excellent charging characteristics, can form a clear and high-resolution image, and is stable over time. Provided are a charge control agent that can be maintained charged and excellent in environmental stability, a method for producing a charge control agent that can easily adjust the particle size and particle size distribution, and a toner for developing an electrostatic image containing the charge control agent. The purpose is to do.

（化学式（１）中、Ｒ^１、Ｒ^２、Ｒ^３、及びＲ^４は、同一又は異なり、水素原子、炭素数１〜１８のアルキル基、炭素数１〜１８のアルコキシ基、炭素数２〜１８のアルケニル基、スルホンアミド基、スルホンアルキル基、スルホン酸基、カルボキシ基、カルボキシエステル基、ヒドロキシ基、アセチルアミノ基、ベンゾイルアミノ基、又はハロゲン原子であり、Ｘは水素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、ニトロ基、又はハロゲン原子であり、Ａ^＋は水素イオン、ナトリウムイオン、カリウムイオン、アンモニウムイオン、有機アンモニウムイオン、又はこれらの混合物である）で表される前記アゾ系鉄錯塩のウエットケーキを得る金属化工程と、前記アゾ系鉄錯塩のウエットケーキを、加熱しながらパドルで撹拌することによって乾燥する乾燥工程とを、有するものである。 The method for producing a charge control agent of the present invention, which has been made to achieve the above object, includes a reaction step of obtaining a monoazo compound by a diazotization coupling reaction in a method for producing a charge control agent containing an azo-based iron complex salt, By reacting the monoazo compound with an ironating agent, the following chemical formula (1)

(In Chemical Formula (1), R ¹ , R ² , R ³ , and R ⁴ are the same or different, and are a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or 2 to 2 carbon atoms. 18 alkenyl group, sulfonamido group, sulfonealkyl group, sulfonic acid group, carboxy group, carboxyester group, hydroxy group, acetylamino group, benzoylamino group, or halogen atom, X is hydrogen atom, carbon number 1 to 1 4 is an alkyl group having 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a nitro group, or a halogen atom, and A ⁺ is a hydrogen ion, a sodium ion, a potassium ion, an ammonium ion, an organic ammonium ion, or a mixture thereof) A metallization step for obtaining a wet cake of the azo-based iron complex salt represented, and while heating the wet cake of the azo-based iron complex salt A drying step of drying by stirring at $, and has.

（化学式（２）中、Ｒ^１、Ｒ^２、Ｒ^３、及びＲ^４は、同一又は異なり、水素原子、炭素数１〜１８のアルキル基、炭素数１〜１８のアルコキシ基、炭素数２〜１８のアルケニル基、スルホンアミド基、スルホンアルキル基、スルホン酸基、カルボキシ基、カルボキシエステル基、ヒドロキシ基、アセチルアミノ基、ベンゾイルアミノ基、又はハロゲン原子であり、Ｘは水素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、ニトロ基、又はハロゲン原子である）で表される前記モノアゾ化合物を、前記鉄化剤によって金属化し、前記アゾ系鉄錯塩を得るものであることが好ましい。 In the method for producing a charge control agent, the metallization step is represented by the following chemical formula (2):

(In the chemical formula (2), R ¹ , R ² , R ³ , and R ⁴ are the same or different and are a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or 2 to 2 carbon atoms. 18 alkenyl group, sulfonamido group, sulfonealkyl group, sulfonic acid group, carboxy group, carboxyester group, hydroxy group, acetylamino group, benzoylamino group, or halogen atom, X is hydrogen atom, carbon number 1 to 1 The monoazo compound represented by (4 alkyl group, alkoxy group having 1 to 4 carbon atoms, nitro group, or halogen atom) is obtained by metallization with the ironating agent to obtain the azo iron complex salt. It is preferable.

  In the method for producing the charge control agent, the drying step may be performed under reduced pressure or under vacuum.

  It is preferable that the manufacturing method of a charge control agent performs the said drying process at 60-160 degreeC.

  The method for producing the charge control agent may be performed at 120 to 160 ° C. after the drying step is performed at 60 to 120 ° C. for at least 6 hours from the start thereof.

（化学式（３）中、Ｒ^５、Ｒ^６、Ｒ^７、及びＲ^８は、同一又は異なり、水素原子又は炭素数１〜１８のアルキル基であり、但し少なくとも１つが炭素数１〜１８のアルキル基であり、少なくとも２つが水素原子であり、Ａ^＋は水素イオン、ナトリウムイオン、カリウムイオン、アンモニウムイオン、有機アンモニウムイオン、又はこれらの混合物である）
で表されるアゾ系鉄錯塩を含み、ＣｕＫα特性Ｘ線によるＸ線回折スペクトルのピークを、ブラッグ角２θにおいて少なくとも６．６±０．２°、１０．３±０．２°、１８．３±０．２°、１９．５±０．２°、２１．７±０．２°、及び３１．７±０．２°に有するものである。 The charge control agent of the present invention has the following chemical formula (3)

(In the chemical formula (3), R ⁵ , R ⁶ , R ⁷ , and R ⁸ are the same or different and are a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, provided that at least one alkyl having 1 to 18 carbon atoms. A group, at least two are hydrogen atoms, and A ⁺ is a hydrogen ion, a sodium ion, a potassium ion, an ammonium ion, an organic ammonium ion, or a mixture thereof)
The peak of the X-ray diffraction spectrum by CuKα characteristic X-ray is at least 6.6 ± 0.2 °, 10.3 ± 0.2 °, 18.3 at a Bragg angle 2θ. Those having ± 0.2 °, 19.5 ± 0.2 °, 21.7 ± 0.2 °, and 31.7 ± 0.2 °.

  In the charge control agent, the cumulative frequency of the particle size on the volume basis of the azo-based iron complex salt measured by the laser diffraction / scattering particle size distribution measuring method is 0.6 to 1.1 μm at 10%, and 1 at 50%. It may be 3 to 1.8 μm.

  The charge control agent preferably contains 0.1 to 0.7% of the volatile component of the azo-based iron complex salt.

  Examples of the charge control agent include those in which the azo iron complex salt is a paddle dry product.

  The electrostatic image developing toner of the present invention contains any of the above charge control agents and a toner resin.

  According to the method for producing a charge control agent of the present invention, the particle size can be adjusted and the particle size distribution can be adjusted only by the drying step. Therefore, a charge control agent having a desired particle size and particle size distribution can be easily obtained. And it can be obtained at low cost. The charge control agent obtained by this production method is excellent in negative charge imparting property and stability, and has good dispersibility in the toner resin. Therefore, the charge control agent obtained by this production method is suitable for a toner for developing an electrostatic charge image with a reduced particle size. Excellent stability.

It is a model fragmentary sectional view of the paddle dryer used for the drying process of the manufacturing method of the charge control agent of the present invention. It is a figure which shows the spectrum of the X-ray diffraction of the charge control agent A obtained by the manufacturing method of the charge control agent to which this invention is applied. It is a figure which shows the spectrum of the X-ray diffraction of the charge control agent F obtained by the manufacturing method of the charge control agent which does not apply this invention.

  Examples of the present invention will be described in detail below, but the scope of the present invention is not limited to these embodiments.

  The method for producing a charge control agent of the present invention has at least a drying step of obtaining a powder of an azo-based iron complex salt by drying the wet cake of the azo-based iron complex salt by heating and stirring using a paddle dryer. As a previous step, a reaction step for obtaining a monoazo compound by a diazotization coupling reaction, a metalization step for metallizing the obtained monoazo compound with an ironating agent to obtain an azo-type iron complex salt, and There may be an exchange step of exchanging counterions.

  The reaction step, which is the first step, is a step of diazotizing an aromatic amine having a specific structure by a known method and subjecting a specific naphthol AS derivative to a diazotization coupling reaction to obtain a monoazo compound.

  In the second step, the metallization step, the obtained wet cake-like or dried monoazo compound is dissolved in an aqueous, water-organic solvent-based, or organic solvent-based liquid medium containing iron chloride, iron sulfate, or iron acetate. This is a step of performing metallization by reacting such an ironizing agent. Usually, the counter ion of the azo-based iron complex salt is generated under the influence of the reaction system atmosphere, pH, added acid, base, and the like. The reaction step and the metallization step can be performed in the same reaction apparatus as a continuous reaction.

The ion exchange step, which is the third step, is a step of preparing an azo-based iron complex salt represented by the chemical formula (1) by preparing A ⁺ as a counter ion as necessary. Specifically, the counter ion of the azo-based iron complex salt generated in the metallization step can be exchanged with a desired counter ion (hydrogen ion, sodium ion, potassium ion, ammonium ion, organic ammonium ion, or a mixture thereof). For example, an azo-type iron complex salt having hydrogen ions as counter ions is exchanged with ammonium ions (for example, aqueous ammonia, urea, ammonium sulfate, thiourea, ammonium chloride, etc.) to ammonium ions or mixture ions containing ammonium ions. Can do.

  The drying step, which is the fourth step, is performed by drying the wet cake of the azo-based iron complex salt represented by the chemical formula (1) by stirring with heating using a paddle dryer, and powdering the azo-based iron complex salt. And adjusting the particle size and particle size distribution of the charge control agent containing an azo-based iron complex salt. According to this paddle dryer, a plurality of processes such as a stirring process, a drying process, and a process for adjusting the particle size and particle size distribution can be performed simultaneously.

  A schematic partial cross-sectional view of a paddle dryer 1 suitably used in the present invention is shown in FIG. The paddle dryer 1 connects a cylindrical main body 2, a rotary shaft 3 pivotally supported on the central axis of the main body 2, a rotary shaft 3 and a motor (not shown), and is rotated by the rotational power of the motor. And a belt 4 for rotating the shaft 3.

  The main body 2 is dried by stirring the wet cake of the azo-based iron complex salt while being heated, and charged into the processing chamber 22 for adjusting the particle size and particle size distribution, and steam (in FIG. 1). , A hollow arrow), a jacket 23 for passing the steam introduced from the introduction pipe 24, a drain 27 for discharging the steam, and the processing chamber 22 under reduced pressure or vacuum. An exhaust pipe 25 connected to a decompression device (not shown) such as a vacuum pump, and a discharge port 26 for discharging the charge control agent 5. Lids that can be opened and closed and that keep the processing chamber 22 airtight are attached to the input port 21 and the discharge port 26, respectively. Steam introduced from the introduction pipe 24 circulates between a heating device (not shown) such as a boiler and the paddle dryer 1, and steam at a constant temperature is always supplied to the jacket 23. The jacket 23 is provided so as to surround the processing chamber 22. Thereby, the heat of the high-temperature steam is uniformly transmitted to the processing chamber 22, and the processing chamber 22 is kept at a constant temperature. This heat dries the wet cake of the azo-based iron complex salt.

  A plurality of paddles 31 are attached to the rotating shaft 3 at regular intervals. The paddle 31 has a rod portion 31a extending from the rotary shaft 3 toward the inner wall surface of the processing chamber 22, and a blade portion 31b that is continuous from the rod portion 31a and twisted while forming a flat plate shape. The paddle 31 rotates in the processing chamber 22 with the rotation axis 3 as a central axis.

  A preferred embodiment of the drying process will be described. First, after opening the lid of the inlet 21, the wet cake of the monoazo iron complex salt used in the present invention is put into the processing chamber 22, and the lid of the inlet 21 is closed to keep the processing chamber 22 airtight. The decompression device is operated to decompress the processing chamber 22 to maintain a constant pressure, and then the motor is operated to rotate the paddle 31. Thereby, the wet cake of the monoazo iron complex salt is wound up and stirred while being crushed in contact with the blade portion 31b of the paddle 31. Next, steam is introduced from the introduction pipe 24 into the jacket 23, and the temperature of the processing chamber 22 is raised, and then kept at a constant temperature. Thereby, the rotary shaft 3 and the paddle 31 are heated and kept at the same temperature as the processing chamber 22. After the drying process is completed, the lid of the discharge port 26 is opened and the charge control agent 5 is taken out.

  The pressure of the steam introduced into the jacket 23 is preferably 0.05 to 0.6 MPa, and more preferably 0.1 to 0.55 MPa. The temperature of the processing chamber 22 is preferably 60 to 160 ° C. More preferably, the temperature is 60 to 120 ° C. in the first half of the drying process from the start of the drying process to 6 hours at the shortest, and 120 to 160 ° C. in the second half thereafter. The time when the processing chamber 22 reaches a predetermined temperature is set as the start time of the drying process, and the time is measured therefrom. The number of rotations of the rotating shaft 3 is preferably 1 to 5 rpm, and more preferably 2 to 4 rpm.

  The pressure in the processing chamber 22 is determined so that the temperature in the processing chamber 22 becomes the boiling point of the solvent contained in the wet cake. For example, when the solvent is water, the pressure in the processing chamber 22 is preferably 250 to 20 mmHg. In this case, it is preferable that the pressure of the steam introduced into the jacket 23 is 0.1 MPa. Thereby, drying of a wet cake and adjustment of a particle size and a particle size distribution can be performed reliably. It is preferable that steam having a relatively low temperature of 60 to 120 ° C. is introduced into the jacket 23 in the early stage of drying in the first half of the drying step, and steam having a higher temperature of 120 to 160 ° C. is introduced into the jacket 23 in the latter half. By setting the temperature of the processing chamber 22 stepwise in the drying process, crystals of the azo-type iron complex salt grow uniformly, and the powder of the azo-type iron complex salt having a sharp particle size distribution with less variation in particle size is obtained. Can be obtained. Therefore, since it is not necessary to provide a classification step separately from the drying step, the charge control agent 5 containing an azo-based iron complex salt can be obtained quickly and easily. In addition, when drying a wet cake efficiently, you may perform a drying process only with high temperature steam.

  More preferably, drying is performed by setting the steam pressure to 0.1 MPa in the first half until at least 6 hours have elapsed since the start of the drying process, and in the second half thereafter, the steam pressure is set to 0.5 to 0.00. Change to 6 MPa. It is possible to adjust the particle size efficiently by setting the steam pressure low at the beginning of the drying process, and then the drying process can be performed in a short time by setting the steam pressure high. By adopting such a method, it is possible to perform the particle size adjustment and the drying process quickly and efficiently. In order to raise the temperature of the processing chamber 22, hot water of 60 to 90 ° C. may be introduced into the jacket 23 instead of steam. Alternatively, the drying process may be performed with the processing chamber 22 in a vacuum.

  Examples of the paddle dryer 1 used in the drying process include paddle dryer (NPD) types manufactured by Nara Machinery Co., Ltd .: NPD-1.6W-G, NPD-3W-G, NPD-4W-G, NPD- 5 W-G, NPD-7W-G, NPD-10W-G, NPD-11W-G, NPD-12W-G, NPD-13W-G; single paddle dryer (SPD) manufactured by Nara Machinery Co., Ltd .: SPD- 8, SPD-23; Bono cooler (NBC) manufactured by Nara Machinery Co., Ltd .: NBC-2.5-G, NBC-5-G, NBC-8-G, NBC-11-G, NBC-15 G, NBC-20-G, NBC-25-G, NBC-30-G, NBC-40-G, NBC-50-G, NBC-60-G, NBC-70-G, NBC-80-G, NBC-90 G, NBC-100-G, NBC-120-G, NBC-140-G; Multi-paddle dryer manufactured by Muramatsu Fusen Equipment Co., Ltd .; PC-3400V, PD-5, PD-3000 manufactured by Neotec Co., Ltd. PD-5000V, PB-250V, PD-1500V, PD-1700V; 3000L paddle dryer manufactured by Shigeno Iron Works, 3400L paddle dryer.

  In addition, although an example of a so-called batch-type drying process in which the process from the introduction of the wet cake to the removal of the charge control agent is performed for each predetermined amount has been given, the so-called continuous process in which the process from the introduction of the wet cake to the removal of the charge control agent is performed continuously. You may perform a drying process by a type | formula.

  The reaction step that is the first step, the metallization step that is the second step, and the ion exchange step that is the third step of the method for producing the charge control agent of the present invention will be described.

  The reaction step, which is the first step, is to obtain a monoazo compound by performing a conventional diazotization coupling reaction in a solvent as shown in the following chemical formula (4). The solvent is preferably water, a water-organic solvent mixed solution, or an organic solvent, and more preferably a water-monohydric lower alcohol mixed solution.

（化学式（４）中、Ｒ^１、Ｒ^２、Ｒ^３、及びＲ^４は、同一又は異なり、水素原子、炭素数１〜１８のアルキル基、炭素数１〜１８のアルコキシ基、炭素数２〜１８のアルケニル基、スルホンアミド基、スルホンアルキル基、スルホン酸基、カルボキシ基、カルボキシエステル基、ヒドロキシ基、アセチルアミノ基、ベンゾイルアミノ基、又はハロゲン原子を表わし、Ｘは水素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、ニトロ基又はハロゲン原子である）

(In the chemical formula (4), R ¹ , R ² , R ³ , and R ⁴ are the same or different, and are a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or 2 to 2 carbon atoms. 18 represents an alkenyl group, a sulfonamido group, a sulfonealkyl group, a sulfonic acid group, a carboxy group, a carboxyester group, a hydroxy group, an acetylamino group, a benzoylamino group, or a halogen atom, X is a hydrogen atom, 4 alkyl group, alkoxy group having 1 to 4 carbon atoms, nitro group or halogen atom)

  For example, an aqueous solution in which an aminophenol (diazo component) having a substituent suitable for forming a metal complex salt such as a hydroxyl group is diluted with hydrochloric acid in an aqueous or water-lower alcohol solvent, sodium nitrite (36% Preparation aqueous solution) is added, and the aminophenol is diazotized by stirring at a temperature of 0 to 5 ° C. for 1 to 3 hours to obtain a diazotized solution. Excess nitrous acid is decomposed with sulfamic acid or the like.

  Next, the naphthol AS derivative which may have a substituent is dissolved or finely dispersed in an alkaline aqueous solution, and a diazotization solution is dropped into the solution, and the solution is added in an aqueous or water-lower alcohol solvent at room temperature or low temperature. A diazotization coupling reaction is performed while stirring for a time to obtain a monoazo compound.

  The metallization process, which is the second process, is a process for obtaining an azo iron complex salt by ironizing a monoazo compound as shown in the following chemical formula (5).

（化学式（５）中、Ｒ^１、Ｒ^２、Ｒ^３、及びＲ^４は、同一又は異なり、水素原子、炭素数１〜１８のアルキル基、炭素数１〜１８のアルコキシ基、炭素数２〜１８のアルケニル基、スルホンアミド基、スルホンアルキル基、スルホン酸基、カルボキシ基、カルボキシエステル基、ヒドロキシ基、アセチルアミノ基、ベンゾイルアミノ基、又はハロゲン原子を表わし、Ｘは水素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、ニトロ基又はハロゲン原子であり、Ｂ^＋はアルカリ金属イオン又はアルカリ金属イオンとＨ^＋との混合物である）

(In the chemical formula (5), R ¹ , R ² , R ³ , and R ⁴ are the same or different and are a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or 2 to 2 carbon atoms. 18 represents an alkenyl group, a sulfonamido group, a sulfonealkyl group, a sulfonic acid group, a carboxy group, a carboxyester group, a hydroxy group, an acetylamino group, a benzoylamino group, or a halogen atom, X is a hydrogen atom, 4 is an alkyl group having 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a nitro group or a halogen atom, and B ⁺ is an alkali metal ion or a mixture of an alkali metal ion and H ⁺ )

  The monoazo compound is dispersed or dissolved in a solvent, and an ironizing agent is further added to cause an ironification reaction. Thereby, an azo-type iron complex salt having a desired counter ion abundance ratio can be easily obtained. The solvent is preferably water, a water-organic solvent mixed solution, or an organic solvent, and particularly preferably water-monohydric lower alcohol. Examples of the ironizing agent include ferric sulfate, ferrous sulfate, ferric chloride, ferrous chloride, ferric nitrate, iron acetate, and iron lactate. Further, the ironification reaction is preferably carried out at a temperature suitable for the type of solvent, with heating reaction or reflux stirring. The ironification reaction may be performed by adding an additive such as a reaction accelerator or a pH adjuster.

  The amount of the ironating agent is preferably 1/2 to 2 equivalents, more preferably 1/2 to 2/3 equivalents, relative to 1 equivalent of the monoazo compound serving as a ligand.

  Examples of the organic solvent include a hydrophilic organic solvent, an amide solvent, an ether solvent, a ketone solvent, a sulfoxide solvent, and an aromatic hydrocarbon solvent, and among them, a hydrophilic organic solvent is preferable.

  Examples of the hydrophilic organic solvent include ethanol, n-propanol, isopropanol, n-butanol, isobutanol, amyl alcohol, benzyl alcohol, cyclohexanol and diacetone alcohol; ethylene glycol monomethyl ether, ethylene glycol mono Alkyl ethers of glycols such as ethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monoethyl ether; ethylene glycol monoacetate, propylene glycol monoacetate, etc. Glycol acetates; ethylene glycol, diethylene glycol Glycols such as alcohol, trimethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, and butanediol. Among these, alcohols or glycols are preferable, alcohols having 1 to 8 carbon atoms or glycols having 2 to 18 carbon atoms are more preferable, and from the viewpoint that the average particle size of the resulting charge control agent can be reduced, the number of carbon atoms is 1 A lower alcohol of ˜6 is more preferred. These may use only 1 type, or may use multiple types, Especially, ethanol, n-propanol, isopropanol, n-butanol, and / or isobutanol are still more preferable.

  The ion exchange step, which is the third step, is a step of obtaining a wet cake of the azo iron complex salt by exchanging the counter ion of the azo iron complex salt obtained in the metallization step with a desired counter ion as necessary. . The pH can be adjusted by adding an acid or base to the reaction solution of the azo-based iron complex salt to obtain an azo-based iron complex salt having a desired counter ion. Examples of the counter ion include hydrogen ion, sodium ion, potassium ion, ammonium ion, organic ammonium ion, or a mixture thereof.

  When the counter ion is a hydrogen ion, the reaction solution of the azo iron complex salt is first dropped into an aqueous solution prepared by diluting an acid such as hydrochloric acid, sulfuric acid, nitric acid, or acetic acid, and the crystals of the azo iron complex salt are dispersed. To obtain a dispersion. By separating the crystals from the dispersion, an azo iron complex salt having hydrogen ions as counter ions can be obtained.

  When the counter ion is an alkali metal ion, first, the reaction solution of the azo type iron complex salt is dropped into an aqueous solution prepared by diluting a base such as sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, or sodium carbonate, A dispersion in which iron complex salt crystals are dispersed is obtained. By separating the crystals from the dispersion, an azo iron complex salt having an alkali metal ion such as sodium ion and / or potassium ion as a counter ion can be obtained.

  When the counter ion is an ammonium ion or a mixture ion containing ammonium ion, the azo iron complex salt having a hydrogen ion as a counter ion is first reexchanged using an ammonium reagent. Thereby, an azo-based iron complex salt having ammonium ions or a mixture ion containing ammonium ions as a counter ion can be obtained. Ammonium agents include ammonia water, ammonium sulfate, ammonium chloride, ammonium phosphate, ammonium nitrate, urea, thiourea, and organic ammonium such as primary organic amine, secondary organic amine, tertiary organic amine, and quaternary ammonium salt. Can be mentioned.

  By combining the conditions such as the amount of the acid, base, and ammonium reagent used for the exchange of the counter ion and the reaction temperature, an azo-based iron complex salt having a mixed ion as the counter ion can be obtained. An azo-based iron complex salt in which 86 mol% or more, particularly 90 mol% or more of the cations in the mixed ions are hydrogen ions or ammonium ions can be easily obtained.

  A filtration step may be performed after the metallization step or after the ion exchange step. In the filtration step, the reaction solution containing the azo iron complex salt obtained in the metallization step (or subsequent alkali treatment) or the ion exchange step is separated by filtration into an azo iron complex salt crystal and a solvent to obtain an azo iron. This is a step of obtaining a complex salt wet cake. Filtration methods include sand filtration, bag filtration, centrifugal filtration; vacuum filtration using Nutsche, Moore filter, disc filter, drum filter, Oliver filter; filter press, sealed leaf filter, sealed The pressure filtration method using a multistage filter can be mentioned. A washing step may be performed after the filtration step. The wet cake of the azo-based iron complex salt is thoroughly washed with water and / or an organic solvent. As the cleaning liquid, water is preferable.

  After passing through said process, the drying process using a paddle dryer is performed. The drying step is preferably performed so that the volatile component of the azo-based iron complex salt is in the range of 0.1 to 0.7%, and is dried in the range of 0.1 to 0.5%. It is more preferable. Since the obtained powder of azo-based iron complex salt, which is a dry paddle product, has a fine particle size, is soft, and has a uniform shape, it can be easily crushed. If necessary, a pulverization process may be performed using a pulverizer such as a jet mill.

  Specific examples of the azo iron complex salt represented by the chemical formula (1) are shown below.

（化学式（１）中、Ｒ^１、Ｒ^２、Ｒ^３、及びＲ^４は、同一又は異なり、水素原子、炭素数１〜１８のアルキル基、炭素数１〜１８のアルコキシ基、炭素数２〜１８のアルケニル基、スルホンアミド基、スルホンアルキル基、スルホン酸基、カルボキシ基、カルボキシエステル基、ヒドロキシ基、アセチルアミノ基、ベンゾイルアミノ基、又はハロゲン原子であり、Ｘは水素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、ニトロ基、又はハロゲン原子であり、Ａ^＋は水素イオン、ナトリウムイオン、カリウムイオン、アンモニウムイオン、有機アンモニウムイオン、又はこれらの混合物である）

(In Chemical Formula (1), R ¹ , R ² , R ³ , and R ⁴ are the same or different, and are a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or 2 to 2 carbon atoms. 18 alkenyl group, sulfonamido group, sulfonealkyl group, sulfonic acid group, carboxy group, carboxyester group, hydroxy group, acetylamino group, benzoylamino group, or halogen atom, X is hydrogen atom, carbon number 1 to 1 4 is an alkyl group, an alkoxy group having 1 to 4 carbon atoms, a nitro group, or a halogen atom, and A ⁺ is a hydrogen ion, a sodium ion, a potassium ion, an ammonium ion, an organic ammonium ion, or a mixture thereof)

In the chemical formula (1), examples of the alkyl group of the substituents R ^{1 to} R ⁴ include a linear or branched alkyl group having 1 to 18 carbon atoms, and more specifically, a methyl group, an ethyl group, and n-propyl. Group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, iso-pentyl group, neo-pentyl group, n-hexyl group, n-heptyl group Group, n-octyl group, 2-ethylhexyl group, n-decyl group, lauryl group and stearyl group. In particular, a linear or branched alkyl group having 1 to 10 carbon atoms is preferable. Furthermore, an iso-butyl group, a sec-butyl group, a tert-butyl group, an iso-pentyl group, and a 2-ethylhexyl group are preferable.

In the chemical formula (1), examples of the alkoxy group of the substituents R ^{1 to} R ⁴ include an alkoxy group having 1 to 18 carbon atoms, and more specifically, a methoxy group, an ethoxy group, an n-propoxy group, and an iso-propoxy group. Group, n-butoxy group, iso-butoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, neo-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy Groups.

In the chemical formula (1), specific examples of the alkenyl group of the substituents R ^{1 to} R ⁴ include a vinyl group, an allyl group, and a propenyl group.

In the chemical formula (1), the halogen atom of the substituents ^{R 1 ~R 4, F, Cl} , Br, and the like I have.

  In the chemical formula (1), the alkyl group of the substituent X includes a linear or branched alkyl group having 1 to 4 carbon atoms. More specifically, a methyl group, an ethyl group, an n-propyl group, an iso- A propyl group, n-butyl group, iso-butyl group, sec-butyl group, and tert-butyl group are mentioned.

  In the chemical formula (1), examples of the alkoxy group of the substituent X include an alkoxy group having 1 to 18 carbon atoms, and more specifically, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n- A butoxy group, an iso-butoxy group, a sec-butoxy group, a tert-butoxy group, and the like can be given.

  In the chemical formula (1), examples of the halogen atom of the substituent X include F, Cl, Br, and I.

  Other specific compounds of the azo-based iron complex salt represented by the chemical formula (1) are exemplified by the compounds represented by Table 1 below. However, the present invention is not limited to these.

  The wet cake of an azo-based iron complex salt is dried by being stirred while being heated in the drying step. Thereby, the crystal form of the azo-based iron complex salt is uniformly adjusted, and a charge control agent having a desired particle size and particle size distribution is obtained.

  As a preferable structure of the chemical formula (1), the following chemical formula (3) may be mentioned.

（化学式（３）中、Ｒ^５、Ｒ^６、Ｒ^７、及びＲ^８は、同一又は異なり、水素原子又は炭素数１〜１８のアルキル基であり、但し少なくとも１つが炭素数１〜１８のアルキル基であり、少なくとも２つが水素原子であり、Ａ^＋は水素イオン、ナトリウムイオン、カリウムイオン、アンモニウムイオン、有機アンモニウムイオン、又はこれらの混合物である）

(In the chemical formula (3), R ⁵ , R ⁶ , R ⁷ , and R ⁸ are the same or different and are a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, provided that at least one alkyl having 1 to 18 carbon atoms. A group, at least two are hydrogen atoms, and A ⁺ is a hydrogen ion, a sodium ion, a potassium ion, an ammonium ion, an organic ammonium ion, or a mixture thereof)

In the chemical formula (3), examples of the alkyl group of the substituents R ^{5 to} R ⁸ include a linear or branched alkyl group having 1 to 18 carbon atoms, and more specifically, a methyl group, an ethyl group, and n-propyl. Group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, iso-pentyl group, neo-pentyl group, n-hexyl group, n-heptyl group Group, n-octyl group, 2-ethylhexyl group, n-decyl group, lauryl group and stearyl group. In particular, a linear or branched alkyl group having 1 to 10 carbon atoms is preferable. Furthermore, an iso-butyl group, a sec-butyl group, a tert-butyl group, an iso-pentyl group, and a 2-ethylhexyl group are preferable.

In the chemical formula (3), examples of the organic ammonium ion of the counter ion A ⁺ include those obtained by an ammonium agent such as a primary organic amine, a secondary organic amine, a tertiary organic amine, and a quaternary ammonium salt.

  The charge control agent containing an azo-based iron complex salt represented by the chemical formula (3) has a major peak of X-ray diffraction by CuKα characteristic X-ray at least 6.6 ± 0.2 ° at Bragg angle 2θ, 10.3. Major peaks at ± 0.2 °, 18.3 ± 0.2 °, 19.5 ± 0.2 ° and 21.7 ± 0.2 °, and further to 31.7 ± 0.2 ° Has a peak. This charge control agent exhibits a uniform and stable chargeability, and when an electrostatic charge image developing toner containing the charge control agent is developed, a high-resolution image can be formed, and the charge control agent can be stably charged over time. Can be maintained.

  The charge control agent containing an azo-based iron complex salt represented by the chemical formula (3) is adjusted in particle size and particle size distribution through a drying process. The particle diameter D10 value when the cumulative frequency of the particle diameter on the volume basis of the azo-based iron complex salt measured by the laser diffraction / scattering particle size distribution measuring method is 10% is preferably 0.6 to 1.1 μm, 0 More preferably, it is 7 to 1.0 μm. The particle diameter D50 value (median diameter) at 50% is preferably 1.3 to 1.8 μm, and more preferably 1.3 to 1.7 μm. Furthermore, the volatile component of the azo-based iron complex salt is preferably in the range of 0.1 to 0.7%.

  The charge control agent containing an azo-based iron complex salt represented by the chemical formula (3) includes a metallization step of metallizing a monoazo compound represented by the following chemical formula (6) with an ironating agent to obtain an azo-based iron complex salt; The obtained azo-type iron complex salt wet cake is preferably obtained by a production method having a drying step of stirring and drying with a paddle while heating.

（化学式（６）中、Ｒ^５、Ｒ^６、Ｒ^７、及びＲ^８は、同一又は異なり、水素原子又は炭素数１〜１８のアルキル基であり、但し少なくとも１つが炭素数１〜１８のアルキル基であり、少なくとも２つが水素原子である）

(In the chemical formula (6), R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same or different and are a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, provided that at least one is an alkyl having 1 to 18 carbon atoms. A group, at least two of which are hydrogen atoms)

  The charge control agent containing an azo-based iron complex salt represented by the chemical formula (1) and / or (3) is used, for example, in an electrostatic image developing toner. This toner for developing an electrostatic charge image contains, for example, 0.1 to 10 parts by weight of a charge control agent and 0.5 to 10 parts by weight of a colorant with respect to 100 parts by weight of a resin for toner. . Such a toner for developing an electrostatic image develops a charge quickly when developing an electrostatic latent image at a low speed or a high speed. Furthermore, a sufficient amount of charge can be charged, and charging can be stably maintained.

  For example, the toner for developing an electrostatic image is manufactured as follows. The toner binder resin, colorant and charge control agent, and additives such as magnetic materials and fluidizing agents, if necessary, are thoroughly mixed using a ball mill or other mixer, and then heated rolls, kneaders, and extruders. The toner for developing an electrostatic charge image having an average particle diameter of 5 to 12 μm is obtained by melt-kneading using such a heat kneader, cooling and solidifying, pulverizing and classifying.

  Also, a method obtained by dispersing the material in the binder resin solution and then spray drying, a predetermined material mixed with the monomer to constitute the binder resin to form an emulsified suspension, and then the polymerized toner The toner for developing an electrostatic charge image can also be obtained by a polymerization toner production method (for example, methods described in JP-A-1-260461 and JP-A-2-32365).

  The electrostatic image developing toner can be used as a two-component developer. In that case, a developer is prepared by mixing the toner and carrier powder. This developer is used when developing by, for example, a two-component magnetic brush developing method.

  Any known carrier powder can be used and is not particularly limited. Specifically, iron powder, nickel powder, ferrite powder, and glass beads having a particle size of about 50 to 200 μm may be used, and the surfaces of these may be acrylic acid ester copolymers, styrene-acrylic acid ester copolymers, silicones. It may be coated with a resin, a polyamide resin, a fluorinated ethylene resin, or the like.

  The electrostatic image developing toner can be used as a one-component developer. In that case, when the toner is produced as described above, for example, a fine powder made of a ferromagnetic material such as iron powder, nickel powder, ferrite powder or the like is added and dispersed to prepare a developer. This developer is used when developing by, for example, a contact developing method, a jumping developing method or the like.

  As the binder resin for toner contained in the electrostatic image developing toner, known synthetic resins and natural resins are used. The binder resin is, for example, a homopolymer of styrene such as polystyrene, poly-p-chlorostyrene, polyvinyltoluene, or a substituted product thereof; styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene. -Vinyl naphthalene copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer Styrene copolymer such as polymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer Coalescence is mentioned. Examples of the comonomer for the styrene monomer of the styrene copolymer include, for example, acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, and acrylic acid. Monocarboxylic acids having double bonds such as phenyl, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, acrylonitrile, acrylamide, and substituted products thereof; maleic acid, butyl maleate, maleic acid Dicarboxylic acids having a double bond such as methyl and dimethyl maleate, and their substitutes; Vinyl esters such as vinyl chloride, vinyl acetate and vinyl benzoate; Ethylene-based olefins such as ethylene, propylene and butylene Down like; vinyl methyl ketone, vinyl ketones such as vinyl hexyl ketone, vinyl methyl ether, vinyl ethyl ether, vinyl ethers such as vinyl isobutyl ether. These may be used alone or in combination.

  The binder resin may be a styrene resin crosslinked with a crosslinking agent. As the crosslinking agent, compounds having two or more polymerizable double bonds are mainly used, and aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,3- Carboxylic acid ester having two double bonds such as butanediol dimethacrylate; divinyl aniline, divinyl ether, divinyl sulfide, divinyl sulfone divinyl compound; compounds having three or more vinyl groups. These may be used alone or in combination.

  The binder resin is polyvinyl chloride, phenol resin, natural modified phenol resin, natural resin modified maleic acid resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane resin, xylene resin, polyamide resin, furan It may be a resin, epoxy resin, polyvinyl butyral, terpene resin, coumarone indene resin, or petroleum resin.

  The toner for developing an electrostatic image may contain a known dye or pigment as a colorant. Examples of the colorant include carbon black (for example, acetylene black, lamp black, thermal black, furnace black, channel black, ketjen black, etc.), titanium black, and black iron oxide.

  The electrostatic image developing toner may further contain a release agent. Release agents include low molecular weight polyolefin waxes such as polyethylene, polypropylene, and polybutene; silicone waxes; fatty acid amides such as oleic acid amide and stearic acid amide; plant waxes; animal waxes such as beeswax; minerals and petroleum Synthetic waxes such as ester waxes.

  Examples of plant waxes include carnauba wax, rice wax, and candelilla wax, and carnauba wax is preferred. Examples of the mineral / petroleum wax include montan wax, paraffin wax, and Fischer-Tropsch wax, and paraffin wax is preferred.

  These release agents can be used alone or in combination. The addition amount is preferably 0.3 to 15% by weight. When the addition amount of the release agent is less than 0.3% by weight, it does not sufficiently act as a release agent when fixing an image. On the other hand, if it exceeds 15% by weight, the exposure of the release agent on the toner surface increases, resulting in charging failure, toner scattering from the developer carrying member and image quality degradation, adhesion between toner particles, layer Since the interaction with the forming member and the developer carrying member becomes large, the cleaning property is lowered.

The electrostatic image developing toner may contain a magnetic toner containing a magnetic material. Examples of the magnetic material include metal oxides containing elements such as iron, cobalt, nickel, copper, magnesium, manganese, and zinc. These magnetic materials are preferably magnetic powders having a BET (Brunauer-Emmett-Teller) specific surface area of 1 to 20 m ² / g by a nitrogen adsorption method and a Mohs hardness of 5 to 7. Examples of the shape of the magnetic material include octahedron, hexahedron, spherical shape, needle shape, and flake shape, but those having low anisotropy such as octahedron, hexahedron, and spherical shape are preferable. Those having an isotropic shape can achieve good dispersion even with respect to the binder resin and wax in the toner. The average particle size of the magnetic material is preferably 0.05 to 1.0 μm.

  This magnetic material is preferably contained in an amount of 50 to 200 parts by weight, more preferably 70 to 150 parts by weight, based on 100 parts by weight of the binder resin for toner. When the amount is less than 50 parts by weight, the toner transportability is insufficient, and the developer layer on the developer carrying member is uneven, which tends to cause image unevenness, and the image density caused by excessive increase in the charge of the developer. Decrease is likely to occur. On the other hand, when the amount exceeds 200 parts by weight, the developer cannot be sufficiently charged, and the image density tends to be lowered.

  The toner for developing an electrostatic image may contain an inorganic fine powder or a hydrophobic inorganic fine powder in order to improve environmental stability, charging stability, developability, fluidity, and storage stability. Examples of such powders include silica fine powder, titanium oxide fine powder, and hydrophobized products thereof. These powders may be used alone or in combination.

Silica fine powder consists of dry silica produced from silicon halide by vapor phase oxidation called dry method; dry silica called fumed silica; metal halide compounds such as aluminum chloride and titanium chloride and silicon by dry method. Dry silica in which a composite fine powder of silica and another metal oxide is produced from a halogen compound; so-called wet silica produced from water glass or the like is used. Among them, dry silica is preferable because it has few silanol groups on the surface and inside, and few production residues such as Na ₂ O and SO ₃ ²⁻ .

  The silica fine powder is preferably hydrophobized. The hydrophobization treatment is a treatment with an organosilicon compound that reacts or physically adsorbs with silica fine powder. Preferably, a dry fine powder produced by vapor phase oxidation of a silicon halogen compound is treated with a silane cup. This is a method of treating with an organosilicon compound such as silicone oil after treating with a ring agent or simultaneously with treating with a silane coupling agent.

  Examples of silane coupling agents used for hydrophobizing treatment include hexamethylene disilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane. Benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilylacrylate, vinyldimethylacetoxysilane, Dimethyldiethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-dibi Nyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane, and dimethylpolysiloxane containing 2 to 12 siloxane units per molecule and containing hydroxyl groups bonded to one silicon atom in each terminal unit Examples include siloxane.

  Examples of the organosilicon compound include silicone oil. Preferred silicone oils include dimethyl silicone oil, methylphenyl silicone oil, α-methylstyrene modified silicone oil, chlorophenyl silicone oil, and fluorine modified silicone oil.

  The electrostatic image developing toner may contain an external additive as required. Examples of external additives include inorganic particles such as silica, aluminum oxide (alumina), zinc oxide, tin oxide, barium titanate, strontium titanate; organic acid salt particles such as zinc stearate and calcium stearate; Examples thereof include organic resin particles such as coalescence particles, acrylic acid ester polymer particles, styrene-methacrylic acid ester copolymer particles, and styrene-acrylic acid ester copolymer particles. Examples of the external additive include a charging aid, a conductivity imparting agent, a fluidity imparting agent, an anti-caking agent, a release agent at the time of fixing with a heat roller, a lubricant, an abrasive, and a developability improver.

  Examples of the fluidity-imparting agent include silica, titanium oxide, and aluminum oxide. Among them, a hydrophobic one is preferable. Examples of the lubricant include polytetrafluoroethylene, zinc stearate, and polyvinylidene fluoride. Examples of the abrasive include cerium oxide, silicon carbide, and strontium titanate.

  Examples of the conductivity imparting agent include carbon black, zinc oxide, antimony oxide, and tin oxide. A small amount of reverse-polarity white fine particles and black fine particles are used as the developability improver.

  EXAMPLES Next, although an Example is given and this invention is demonstrated more concretely, this invention is not limited only to these.

(Preparation Example 1: Charge Control Agent A)
(1. Preparation of charge control agent A)
Charge control agent A was prepared as follows.
(1) Reaction process (synthesis of monoazo compounds)
95 kg of concentrated hydrochloric acid was diluted with 150 L of water, and 45 kg of 2-amino-4-tert-butylphenol was added thereto for dissolution, and then cooled to 5 ° C. with 150 kg of ice. Diazotization reaction was performed by gradually adding 49 kg of 40% sodium nitrite aqueous solution to obtain a diazonium salt. Separately, 70 kg of naphthol AS and 60 kg of 48% potassium hydroxide aqueous solution were added to 280 L of water and dissolved. To this, a diazonium salt solution and 40 kg of n-butanol were added dropwise and reacted at 80 ° C. for 2 hours. After the reaction, the mixture was filtered and washed with a centrifugal separator to obtain 275 kg of a monoazo compound wet cake.

(2) Metallization process (synthesis of azo-based iron complex salts)
The whole wet cake of the monoazo compound obtained in the reaction step was added to 1000 L of water, and 90 kg of 48% potassium hydroxide aqueous solution and 80 kg of n-butanol were added and dispersed at 80 ° C. After dispersion, 130 kg of 40% ferric sulfate aqueous solution was added dropwise. The pH of the reaction solution at this time was 2.8. Reaction was performed at 80 degreeC for 6 hours, and the azo iron complex salt was obtained. After the reaction, the mixture was filtered and washed with a press filter to obtain 312 kg of a wet cake of azo-based iron complex salt.

(3) Drying process (Drying of azo-based iron complex salt)
The whole amount of the wet cake of the azo-based iron complex salt obtained in the metallization step was put into a paddle dryer (manufactured by Neotec Co., Ltd., product name: PD-1500V), and the pressure in the processing chamber of the paddle dryer was reduced to 60 mmHg. Steam in a paddle dryer was heated to 70 ° C. by introducing and circulating steam with a vapor pressure of 0.1 MPa into the jacket of the paddle dryer. In the first half of 6 hours after reaching this temperature, the rotating shaft of the paddle dryer was rotated at 4 rpm to dry the wet cake. At this time, the treatment chamber was kept at 100 mmHg to 200 mmHg until most of the water was distilled off. In the second half after 6 hours, the charge control agent A was prepared by increasing the vapor pressure to 0.55 MPa to bring the treatment chamber to 120 ° C. and stirring for 24 hours.

(2. Analysis and evaluation of charge control agent A)
(Measurement 1) Measurement of average particle diameter Charge control agent A 5 mg which is an aggregated particle is added to a 5 v / v% solution of an activator (manufactured by Kao Corporation, product name: MORE) to form a mixed solution and subjected to ultrasonic vibration for 5 minutes. It was. 0.25 mL of this mixed solution was put into a particle size distribution measuring device (manufactured by Horiba, Ltd., product name: LA-950), further subjected to ultrasonic vibration for 5 minutes and finely dispersed, and then the particle size distribution was measured. The D10 value represents the particle diameter when the cumulative frequency on the volume basis shows 10%, and the D50 value represents the particle diameter (median diameter) when the cumulative frequency on the volume basis shows 50%. The charge control agent A had a D10 value of 0.89 μm and a D50 value of 1.56 μm.

(Measurement 2) Analysis of counter ion Measurement of hydrogen ion amount, Na ion amount and K ion amount Using atomic absorption spectrometer (manufactured by Varian Technologies Japan Limited, product name: SpectrAA-220FS), Na in charge control agent A As a result of measuring the K content, hydrogen ions were 99.7%, the Na ion content was 0%, and the K ion content was 0.3%.

(Measurement 3) Measurement of pH 5 g of charge control agent A was dispersed in 100 mL of ion-exchanged water, and the weight at that time was recorded. This was boiled and extracted to extract ionic components and filtered after extraction. Ion exchange water was added until the weight of the filtrate was the same as the initial weight, and the pH of this solution was measured with a pH meter (product name: HM30R, manufactured by Toa DKK Corporation). As a result, the pH of the charge control agent A was 6 .2.

(Measurement 4) Measurement of electrical conductivity Charge control agent A5g was disperse | distributed to 500 mL ion-exchange water, and the weight in that case was recorded. This was boiled and extracted to extract ionic components and filtered after extraction. Ion exchange water was added until the weight of the filtrate was the same as the initial weight, and the electrical conductivity of this solution was measured with an electric conductivity meter (product name: AOL-10, manufactured by Toa DKK Corporation). The electric conductivity of the agent A was 167 μS / cm.

(Measurement 5) Measurement of Volatile Component Charge control agent A2 g was added to a weighing bottle (weight a), and the total weight (weight b) was measured. The weighing bottle was placed in a hot air drier maintained at 107 ° C., allowed to stand for 2 hours, and then allowed to cool to room temperature in a desiccator containing a desiccant. After standing to cool, measure the weight of the weighing bottle (weight c),
Volatile component (%) = {(ba)-(ca)} / (ba) × 100
As a result of obtaining the volatile component by the following formula, the volatile component of the charge control agent A was 0.23%.

(Measurement 6) Measurement of ash content Charge control agent A1g was put into the crucible (weight a), and the total weight (weight b) was measured. The crucible was placed in an electric furnace maintained at 800 ° C. and left for 2 hours, and then allowed to cool to room temperature in a desiccator containing a desiccant. Measure the weight (weight c) of the crucible after standing to cool,
Ash content (%) = (ca) / (ba) × 100
As a result of obtaining the ash content by the following formula, the ash content of the charge control agent A was 8.72%.

(Measurement 7) Measurement of X-ray diffraction pattern A powder X-ray diffraction pattern was measured under the following conditions.
Equipment used: X-ray diffractometer (Rigaku Corporation, product name: RINT TTRIII)
X-ray source: Cu
Tube voltage, tube current: 50.0kV, 300mA
Divergent slit: 2/3 °
Receiving slit: 0.30mm
Scattering slit: 2/3 °
Scanning speed: 4.0 ° / min
Sampling width: 0.02 °
Scanning range: 5.0-40.0 °
Peak search conditions: second derivative method, peak width threshold 0.2 °, peak intensity threshold 600 cps

  As a result, the X-ray diffraction pattern of the charge control agent A is 6.6 °, 10.3 °, 18.3 °, 19.5 ° and 21.7 ° at a Bragg angle 2θ as shown in FIG. A peak was confirmed at 31.7 ° together with the main peak.

(Preparation Example 2: Charge control agent B)
In the first half of the drying step of Preparation Example 1, charge control agent B was prepared in the same manner as Preparation Example 1, except that the drying time was 10 hours. When the X-ray diffraction of the obtained charge control agent B was measured, it was found to be 31.7 ° with major peaks at 6.6 °, 10.3 °, 18.3 °, 19.5 °, 21.7 °. A peak was confirmed.

(Preparation Example 3: Charge control agent C)
In the first half of the drying step of Preparation Example 2, charge control agent C was prepared in the same manner as Preparation Example 2, except that the pressure in the processing chamber was 30 mmHg. When the X-ray diffraction of the obtained charge control agent C was measured, it was found to be 31.7 ° with major peaks at 6.6 °, 10.3 °, 18.3 °, 19.5 °, 21.7 °. A peak was confirmed.

(Preparation Example 4: Charge control agent D)
In the latter half of the drying step of Preparation Example 1, a charge control agent D was prepared in the same manner as Preparation Example 1, except that the vapor pressure was 0.6 MPa. When X-ray diffraction of the obtained charge control agent D was measured, it was found to be 31.7 ° with major peaks at 6.6 °, 10.3 °, 18.3 °, 19.5 °, 21.7 °. A peak was confirmed.

(Preparation Example 5: Charge control agent E)
Charge control agent E was prepared in the same manner as in Preparation Example 2, except that it continued for 48 hours in the latter half of the drying step in Preparation Example 2. When X-ray diffraction of the obtained charge control agent E was measured, it was found to be 31.7 ° with major peaks at 6.6 °, 10.3 °, 18.3 °, 19.5 °, 21.7 °. A peak was confirmed.

  About charge control agent B-E, it carried out similarly to the charge control agent A (measurement 1) measurement of average particle diameter-(measurement 6) ash content was measured. The results are shown in Table 2.

(Comparative Preparation Example 1: Charge Control Agent F)
(1) Synthesis of monoazo compound 95 kg of concentrated hydrochloric acid was diluted with 150 L of water, and 45 kg of 2-amino-4-tert-butylphenol was added thereto for dissolution, followed by cooling to 5 ° C. with 150 kg of ice. Diazotization reaction was performed by gradually adding 49 kg of 40% sodium nitrite aqueous solution to obtain a diazonium salt. Separately, 70 kg of naphthol AS and 60 kg of 48% potassium hydroxide aqueous solution were added to 280 L of water and dissolved. To this, a diazonium salt solution and 40 kg of isobutanol were added dropwise and reacted at 80 ° C. for 2 hours. After the reaction, the mixture was filtered and washed with a centrifuge to obtain 281 kg of a wet cake.

(2) Synthesis of azo-based iron complex salt The whole wet cake of the obtained monoazo compound was added to 1000 L of water, and 90 kg of 48% potassium hydroxide aqueous solution and 80 kg of isobutanol were added and dispersed at 80 ° C. After dispersion, 130 kg of 40% ferric sulfate aqueous solution was added dropwise. The pH of the reaction solution at this time was 2.6. Reaction was performed at 80 degreeC for 6 hours, and the azo iron complex salt was obtained. After the reaction, the mixture was filtered and washed with a press filter to obtain 309 kg of a wet cake.

(3) Drying of azo-based iron complex salt After transferring the entire amount of the obtained wet cake to a metal tray, it was put into a shelf-type hot air dryer and dried at an internal temperature of 120 ° C. for 24 hours. Prepared.

  X-ray diffraction of the obtained charge control agent F was measured. The results are shown in FIG. As shown in the figure, peaks were detected at 6.6 °, 10.3 °, 18.3 °, 19.5 °, and 21.7 °, but there was no peak at 31.7 °.

  Further, the charge control agent F was analyzed and evaluated in the same manner as the charge control agent A in the preparation examples. The results are shown in Table 2.

  As shown by the D10 value and D50 value in Table 2, the charge control agents A to E of Preparation Examples 1 to 5 had a small variation in particle size and a very narrow particle size distribution. It was found that the charge control agent F of Comparative Preparation Example 1 had a large variation in particle size and a wide particle size distribution.

  Next, electrostatic charge image developing toners to which the present invention is applied are prepared using the charge control agents A to E, respectively, and electrostatic charge image developing toners to which the present invention is not applied are applied using the charge control agent F. Prepared. These toners were measured for triboelectric charge and evaluated for environmental stability of charge.

Example 1
100 parts by weight of styrene-acrylic copolymer resin (manufactured by Mitsui Chemicals, product name: CPR-100) and 2 parts by weight of low molecular weight polypropylene (manufactured by Sanyo Chemical Industries, product name: Viscol 550-P) Then, 6 parts by weight of carbon black (manufactured by Mitsubishi Chemical Corporation, product name: MA100) and 1 part by weight of the charge control agent A were uniformly premixed with a high-speed mixer. Next, it was melt-kneaded (temperature 130 ° C.) with a kneader (manufactured by Kurimoto Steel Co., Ltd., product name: S1KRC twin-screw kneading extruder), cooled, and then coarsely pulverized with a rotor mill (manufactured by Retsch, product name: ZM1). . The resulting coarsely pulverized product was finely pulverized using an air jet mill equipped with a classifier (manufactured by Seishin Enterprise Co., Ltd., product name: CO-JET System α) to obtain a toner having a particle size of 10 μm.

  A developer was prepared by mixing 95 parts by weight of a ferrite carrier (product name: F-150, manufactured by Powder Tech Co., Ltd.) with 5 parts by weight of the obtained toner.

The developer is weighed in a plastic bottle and stirred with a ball mill at a rotation speed of 100 rpm to charge the developer. The initial charge amount under atmospheric conditions (3-minute value) and the triboelectric charge amount per stirring time (minute) Was measured and the stability of charging was evaluated. The stability of charging was evaluated in two stages, with ○ indicating a stable one and × indicating no. In addition, the charge amount (10 minutes value) was measured in the same manner for a developer conditioned for 24 hours or more under the standard conditions of 25 ° C. and 50% relative humidity, whereas low temperature and low humidity (10 ° C., relative humidity) 30%) and high-temperature and high-humidity (30 ° C, relative humidity 80%) Developers conditioned for more than 24 hours under the same conditions, the charge amount is measured in the same manner, and the charge amount environment stability is also evaluated at the same time. did. Regarding environmental stability of charge amount,
{[(Charge amount under standard conditions) − (Charge amount under low temperature and low humidity)] / (Charge amount under standard conditions)} × 100
as well as
{[(Charge amount under standard conditions) − (Charge amount under high temperature and high humidity)] / (Charge amount under standard conditions)} × 100
The value was determined according to the formula of 、, the absolute value of the rate of change was 0.0 to 5.0%, ◯, 5.0 to 10.0% was △ 10.0% or more The evaluation was made in three stages, with the item x. The results are shown in Table 3.

  The charge amount was measured by a blow-off charge amount measuring machine (Kyocera Chemical Co., Ltd., product name: TB-200).

  A toner image was formed with a commercially available copying machine using this developer. The obtained toner image was visually observed for fogging, fine line reproducibility, charging stability and sustainability, and offset phenomenon.

  As for fog, ○ indicates that there is no fog, X indicates that there is no fog, and as for thin line reproducibility, ○ indicates that the reproducibility is not good, and X indicates that the reproducibility is poor. Evaluation was made in two stages, with ○ indicating that the property and durability were good, and × indicating bad, and regarding the offset phenomenon, ○ indicating that the offset phenomenon was not observed and × indicating the observed offset phenomenon. The results are shown in Table 3.

  As is apparent from Table 3, the developers of the examples were excellent in charging stability and sustainability, and further excellent in environmental stability. Further, the toner image formed using the toner image was free from fogging, excellent in fine line reproducibility, charging stability and sustainability, and no offset phenomenon was observed. On the other hand, the developer of the comparative example had a large average particle diameter of the charge control agent made of an azo-based iron complex salt, and the charge control agent caused poor dispersion in the toner, so that the rising characteristics were inferior. In addition, the environmental stability was poor compared to the charge control agents of the examples, and it was not suitable for use under high-temperature and high-humidity conditions such as in summer or when the temperature and humidity fluctuated.

  The charge control agent obtained by the production method of the present invention has a uniform shape and particle size and is finely dispersed. For this reason, the charge rise is fast, the charge controllability is uniform, the charge maintaining property is high, and when used as a toner for developing an electrostatic image, the toner has no fog, and fine line reproducibility, charge stability and sustainability. Is excellent. It can also be used for powder coatings used for electrostatic powder coating.

  The electrostatic charge image developing toner containing this charge control agent has a rapid rise in charge. In this toner, the charge control agent is uniformly dispersed in the toner, and the toner can be stably charged for a long time with a uniform and high charge amount by being charged to a negative charge. It is stable, clear and has high resolution and is beautiful without fog.

  1 is a paddle dryer, 2 is a main body, 3 is a rotating shaft, 4 is a belt, 5 is a charge control agent, 21 is a charging port, 22 is a processing chamber, 23 is a jacket, 24 is an introduction pipe, 25 is an exhaust pipe, 26 Is a drain, 27 is a drain, 31 is a paddle, 31a is a rod portion, and 31b is a blade portion.

Claims (10)

In a method for producing a charge control agent containing an azo-based iron complex salt,
A reaction step of obtaining a monoazo compound by a diazotization coupling reaction;
By reacting the monoazo compound with an ironating agent, the following chemical formula (1)

(In Chemical Formula (1), R ¹ , R ² , R ³ , and R ⁴ are the same or different, and are a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or 2 to 2 carbon atoms. 18 alkenyl group, sulfonamido group, sulfonealkyl group, sulfonic acid group, carboxy group, carboxyester group, hydroxy group, acetylamino group, benzoylamino group, or halogen atom, X is hydrogen atom, carbon number 1 to 1 4 is an alkyl group, an alkoxy group having 1 to 4 carbon atoms, a nitro group, or a halogen atom, and A ⁺ is a hydrogen ion, a sodium ion, a potassium ion, an ammonium ion, an organic ammonium ion, or a mixture thereof)
A metallization step of obtaining a wet cake of the azo-based iron complex salt represented by:
A drying step of drying the wet cake of the azo-based iron complex salt by stirring with a paddle while heating,
A method for producing a charge control agent, comprising: The metallization step is represented by the following chemical formula (2)

(In the chemical formula (2), R ¹ , R ² , R ³ , and R ⁴ are the same or different and are a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or 2 to 2 carbon atoms. 18 alkenyl group, sulfonamido group, sulfonealkyl group, sulfonic acid group, carboxy group, carboxyester group, hydroxy group, acetylamino group, benzoylamino group, or halogen atom, X is hydrogen atom, carbon number 1 to 1 4 alkyl groups, alkoxy groups having 1 to 4 carbon atoms, nitro groups, or halogen atoms)
The method for producing a charge control agent according to claim 1, wherein the monoazo compound represented by the formula is metallized with the ironating agent to obtain the azo-based iron complex salt.   The method for producing a charge control agent according to claim 1, wherein the drying step is performed under reduced pressure or under vacuum.   The said drying process is performed at 60-160 degreeC, The manufacturing method of the charge control agent of Claim 1 characterized by the above-mentioned.   2. The method for producing a charge control agent according to claim 1, wherein the drying step is performed at 60 to 120 ° C. for at least 6 hours from the start of the drying step, and then at 120 to 160 ° C. 3. The following chemical formula (3)

(In the chemical formula (3), R ⁵ , R ⁶ , R ⁷ , and R ⁸ are the same or different and are a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, provided that at least one alkyl having 1 to 18 carbon atoms. A group, at least two are hydrogen atoms, and A ⁺ is a hydrogen ion, a sodium ion, a potassium ion, an ammonium ion, an organic ammonium ion, or a mixture thereof)
The peak of the X-ray diffraction spectrum by CuKα characteristic X-ray is at least 6.6 ± 0.2 °, 10.3 ± 0.2 °, 18.3 at a Bragg angle 2θ. Charge control agents characterized by having ± 0.2 °, 19.5 ± 0.2 °, 21.7 ± 0.2 °, and 31.7 ± 0.2 °.   The cumulative frequency of the particle size on a volume basis of the azo-based iron complex salt measured by the laser diffraction / scattering particle size distribution measuring method is 0.6 to 1.1 μm at 10%, and 1.3 to 1 at 50%. The charge control agent according to claim 6, wherein the charge control agent is 8 μm.   The charge control agent according to claim 6 or 7, wherein a volatile component of the azo-based iron complex salt is 0.1 to 0.7%.   The charge control agent according to any one of claims 6 to 8, wherein the azo-based iron complex salt is a paddle dry product.   An electrostatic charge image developing toner comprising the charge control agent according to claim 6 and a resin for toner.

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